Environmentally Friendly Biosorbent from Moringa Oleifera Leaves for Water Treatment

Transcription

1 Environmentally Friendly Biosorbent from Moringa Oleifera Leaves for Water Treatment Eman N. Ali, Sabreen R. Alfarra, Mashita Mohd Yusoff, and Md Lutfor Rahman Abstract In this study Moringa oleifera leaves (biosorbent) is used for Cadmium (II) removal from water as a natural alternative for synthetic sorbents. Synthetic water was used to find optimum conditions for water treatment using biosorbent. The effect of biosorbent dosage and particle size, contact time, and ph effect were studied. Atomic Absorption Spectroscopy (AAS) was used to monitor the Cd (II) concentration before and after treatment with biosorbent. Fourier Transform Infrared Spectroscopy (FTIR) was used to monitor biosorbent structure changes before and after loading with Cd (II). Many parameters were studied such as: dosage of biosorbent (1 10 g/l), contact time (2 20 min), particle size (2 mm, 1 mm, 500 µm, 250 µm, and <250 µm), ph range (4-10), and Cd (II) concentrations (1, 3, 5, and 7 ppm). The statistical analysis of studied parameters showed that all parameters has an effect on Cd (II) removal with p values <0.05 except ph. FTIR result showed changes in the finger print area of biosorbent functional groups due to adsorption of Cd (II). As a conclusion, Moringa oleifera leaves can be used as an effective, low cost, and environmentally friendly biosorbent for the removal of Cd (II) from water. Index Terms Biosorption, Cadmium (II), Moringa oleifera, water treatment. I. INTRODUCTION Every day, there are thousands of chemicals discharged directly and indirectly into water bodies without further treatment for elimination of the included harmful compounds. Heavy metals are without doubt well thought-out as the most hazardous and harmful metals even if they present as traces in water, since they accumulate in the tissue of living organism. Cd (II) is one of the most toxic and hazardous heavy metal and it is responsible for causing kidney damage, renal disorder, high blood pressure, bone fraction, and destruction of red blood cells [1]. Major sources of Cd (II) in environment are electroplating, industries of pigments, plastic, and metal finishing industries. Removal of Cd (II) from aqueous solutions can be accomplished by several techniques such as chemical precipitation, ion exchange, membrane separation and adsorption. Though, currently used methods contain several restrictions in the removal of Cd (II) from water [2]. Such methods showed to be not effective and not economically possible for the treatment of low heavy metal concentrations [3]. As a result, removal and eliminating of Cd (II) in the polluted water has become a vital mission and essential environmental goal to search for appropriate alternative solutions. Biosorption of Cd (II) by agricultural waste materials is one of these alternative treatment methods, because of its simplicity and availability [4], [5]. Many studies were conducted to develop an effective removal of heavy metals using biosorbents, such as microbial biomass [6], and agricultural waste materials such as: sugar cane bagasse fly ash and peat [7], rice husks and straws [8], soya bean, saw dust, walnut and cotton seeds hull, corn cobs, and banana peels [9]. Recently, researchers are paying attention on the removal of Cd (II) from aqueous solution using adsorbents derived from low-cost tree leaves such as loquat leaves (Eriobotrya japonica) [10], Psidium guajava leaves [11], Maize leaves [12], Ulmus leaves [13], Scolymus hispanicus [14], Ulmus carpinifolia and Fraxinus excelsior tree leaves [15], fig leaves [16], Azadirachta indica (Neem leaves) [17], Olea europaea (Olive leaves) [18], and Prunus vium leaves [19]. In this work, the effect of dosage of Moringa oleifera leaves, contact time, biosorbent particle size, and ph on Cd (II) removal from water was examined. The results of this study can be used to evaluate the efficacy of Moringa oleifera leaves for Cd (II) removal from water and may replace activated carbon in water treatment industry. II. MATERIALS AND METHODS Manucript received June 6, 2014; revised July 20, This work was supported by Research & Innovation Department/ Universiti Malaysia Pahang / Malaysia, under grant #: RDU Eman N. Ali is with the Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia Pahang, Gambang, Kuantan, Pahang, Malaysia ( eman@ump.edu.my). Sabreen R. Alfarra is with Universiti Malaysia Pahang, Gambang, Kuantan, Pahang, Malaysia. Mashita Mohd Yusoff and Md Lutfor Rahman are with the Faculty of Industrial Sciences &Technology, Universiti Malaysia Pahang, Gambang, Kuantan, Pahang, Malaysia. A. Biosorbent Preparation Moringa oleifera leaves were collected from nearby area of Universiti Malaysia Pahang, Kuantan, Pahang, Malaysia. Leaves were dried in sunlight for 1 day. After drying, leaves were grounded using electrical grinder, followed be sieving to different particle size (2 mm, 1 mm, 500 µm, 250 µm, and < 250 µm) then kept in plastic bags at room temperature to be used in the study. B. Synthetic Water Preparation A weight of 5 gm of kaolin, laboratory grade (k g DOI: /IJESD.2015.V

2 Sigma- Aldrich) was dissolved with 500 ml of distilled water. Sodium bicarbonate solution with concentration of 100 mg/l was prepared by adding 100 mg of sodium bicarbonate (Hamburg Chemicals) to 1000 ml of distilled water; Adding 500 ml of the sodium bicarbonate solution to the kaolin. The suspension was stirred for about 1 hour at 200 rpm to achieve a uniform dispersion of kaolin particles. Then it was left for at least 24 hours for complete hydration of the kaolin [20]. The synthetic turbid water was used for biosorption test on Cd (II) removal from water by Moringa oleifera leaves. This stock was diluted a few times to get the turbidity needed for each particular test. C. Biosorption Experiments The jar test is a commonly used method to evaluate coagulation- flocculation processes [21]. Biosorption tests were carried out using the jar test equipment. Six beakers were filled with 500 ml of the synthetic water and known quantity of Cd (II) (0.5, 1.5, 2.5, and 3.5 ml of 1000 mg/l stock solution) were added to 500 ml of synthetic water to get the Cd (II) concentration of (1, 3, 5, and 7 ppm). A different dose of Moringa oleifera leaves of (1 to 10 g) was added to the synthetic water, the sample was mixed with biosorbent at 200 rpm for 60 minutes, the suspension was allowed to settle for 30 minutes then the biosorbent was filtered using Whatman filter paper No. 42. The residual Cd (II) in water was analyzed using AAS at wave length of using an acetylene air flame. A triplicate test was performed for every sample to get average of reproducing results. RE of Cd (II) was calculated using the equation: RE% = [(C o C e ) / C o ] 100, where: C o and C e are the initial and residual concentration of Cd (II) in water (mg/l), respectively [10], [19]. D. Equipments The concentrations of Cd (II) in the solutions before and after biosorption were determined by AAS 400 (Perkin Elmer). The ph of the solution was measured with a (Mettler Toledo) ph meter using combined glass electrode. Turbidity measurement was conducted using (Hach 2100Q) turbidity meter for synthetic water used in the experiments. FTIR (Perkin Elmer) was used to identify the different functional groups present in the Moringa oleifera leaves before and after removing Cd (II). FTIR analyses also used to determine the functional groups which are responsible for the Cd (II) binding with Moringa oleifera leaves. The analysis was carried out using KBr pellet and the spectral range varying from 4000 to 400 cm 1. E. Biosorption Study Adsorption of Cd (II) in synthetic water on Moringa oleifera leaves were examined by different parameters such as dose concentration (1-10 g/l), contact time (2-20 min), particle size (2 mm, 1 mm, 500 µm, 250 µm, and < 250 µm), Cd (II) concentration (1, 3, 5, and 7 ppm). The water ph varied from 4 to 10, the ph of water was adjusted by using 0.1N HCl or 0.1N NaOH without changing the volume of the sample. Multi diluted standards of 1, 3, 5 and 7 ppm of Cd (II) in this study were prepared from standard stock solution (1000 mg/l). III. RESULTS AND DISCUSSION The effect of different parameters was studied and the results showed different RE% with different concentration of Cd (II). A. Biosorbent Dose Effect The biosorbent dosage is an important parameter to determine the capacity of a biosorbent for a given initial concentration. Biosorption of Cd(II) onto Moringa oleifera leaves was studied by adding different dosage of Moringa oleifera leaves from 1 to 10 g/l in the treated water sample using different initial Cd (II) concentration of (1, 3, 5, and 7 ppm) and constant contact time of 60 min. Statistical analysis showed that the dose has an effect on the removal of Cd (II) with different concentration from synthetic water. P value for 1 ppm, 3 ppm, 5 ppm, and 7 ppm were , , and , respectively which is <0.05. Fig. 1 shows the removal efficiency for Cd (II) biosorption by Moringa oleifera leaves at different Cd (II) concentration. The percentage of the metal biosorption sharply increased when the biosorbent dosage increased. This result might be explained by the fact that the biosorption sites increases by increasing the biosorbent dosage [10]. Evidently, the maximum RE for 1 ppm was 81% with optimum dosage of 6 gm/l, while it was 74%, 64% and 72% for the Cd(II) concentration of 3 ppm, 5 ppm, and 7 ppm, with optimum dosage of biosorbent 6 g/l, 5 g/l, and 8 g/l, respectively. Therefore, the determined optimum doses obtained from this part of the experiments were used in the next stages of study. Fig. 1. RE% with different biosorbent dose. B. Contact Time Effect The effect of contact time on the biosorption process was studied within time range from 2 to 20 min at the optimum doses mentioned above for the different Cd (II) concentration. It can be seen from Table I, that the RE was increased by increasing the contact time. RE of 72.1% was achieved for Cd (II) removal with concentration of 1 ppm with p value of Statistical analysis results showed that the time has an effect in the first 20 min with p value of , , and for 3 ppm, 5 ppm, and 7 ppm Cd (II) concentration, and RE of 72%, 68%, and 71%, respectively at 18 min contact time. C. Biosorbent Particle Size Effect The effect of the biosorbent particle size on the biosorption process was studied using different sizes of Moringa oleifera leaves. The particle sizes used in this experiment were (2 166

3 mm, 1 mm, 500 µm, 250 µm, and < 250 µm). It was noted that the RE% was very low when 2 mm and 1 mm material were used, and this was probably due to smaller surface area of the biosorbent. On the other hand, statistical analysis showed that particle sizes of 500 µm, 250 µm, and < 250 µm have an effect on Cd (II) removal with p values < Table II, shows the RE% using different particle sizes. It can be observed that the highest RE% was achieved by applying Moringa oleifera leaves with particle size of < 250 µm to remove 81% of Cd (II) in treated water. Time (min) TABLE I: CONTACT TIME EFFECT ON RE% 1 ppm 3 ppm 5 ppm 7 ppm 2 26% 23% 13% 22% 4 18% 27% 17% 24% 6 20% 11% 18% 23% % 11% 14% 18% 10 20% 19% 18% 21% % 25% 55.50% 14% 14 69% 66% 67% 63% % 65.50% 65.40% 64% 18 71% 72% 68% 71% 20 70% 64% 66.40% 65% Biosorbent TABLE II: PARTICLE SIZE EFFECT ON RE% RE% using different biosorbent particle size Particle size 1 ppm 3 ppm 5 ppm 7 ppm 2 mm 9.10% 9.11% 5.15% 8% 1 mm 10.20% 5.23% 4.57% 13% 500 µm 75.00% 72% 71.00% 66% 250 µm 76.70% 71.20% 76% 76% < 250 µm 81% 74% 64% 72% was also investigated on different water turbidities using the optimum doses mentioned above for each concentration of Cd (II). Table IV shows the different turbidites and the optimum RE% for each Cd (II) concentration. It was found that the optimum RE% was achieved when the water turbidity was 50 NTU with 83.40% at Cd (II) concentration of 1 ppm. TABLE IV: WATER TURBIDITY EFFECT ON RE% Turbidity (NTU) 1 ppm 3 ppm 5 ppm 7 ppm F. FTIR Analysis % 61.60% 61.50% 60.60% % 74% 64% 72% % 62.60% 48.30% 48.30% FTIR was used to investigate the functional groups of Moringa oleifera leaves and Cd (II) loaded on Moringa oleifera leaves. FTIR study was carried out and the spectra are shown in Fig. 2 and 3. The Moringa oleifera leaves display a number of absorption peaks, reflecting their complex nature. The 2D FTIR spectrum (Fig. 2) shows the Moringa oleifera leaves before and after biosorption of Cd (II). Fig. 2A shows that Moringa oleifera leaves in nature has two peaks which is considered as the finger print of Moringa oleifera leaves, while Fig. 2B shows those peaks after biosorption of Cd (II) are merged to be one strong peak, which means that Cd (II) is affecting the Moringa oleifera leaves structure. D. ph Effect The effect of ph on the biosorption of Cd (II) onto biosorbent was studied at ph range of It was found that there is no effect of ph on the biosorption of Cd (II). Table III, shows RE% of Cd (II) was in the range of 55% to 65% and there is no much difference in Cd (II) removal. Statistical analysis showed that ph has no effect because the p value was >0.05. Therefore, ph considered as insignificant factor in water treatment process using Moringa oleifera leaves as biosorbent. ph TABLE III: ph EFFECT ON RE% 1 ppm 3 ppm 5 ppm 7 ppm % 56.65% 60.40% 58.49% % 65% 64.60% 56.95% % 58.30% 64.60% 56.80% % 60% 58.20% 57.87% % 57.79% 58.70% 55.41% % 59.39% 56.59% 57.36% % 58.62% 61.64% 57.56% E. Water Turbidity Effect Moringa oleifera leaves as biosorbent for Cd (II) removal Fig. 2. 2D FTIR spectrum of Moringa oleifera leaves before (A), and after (B) biosorption of Cd (II). Fig. 3 shows 1D FTIR for a comparison of the transmittance of Moringa oleifera leaves contents before and after biosorption of Cd (II), the lower graph is the original peaks of Moringa oleifera leaves while the upper is the Moringa oleifera leaves loaded with Cd (II). It shows the absorption peaks at cm -1 and cm -1 were elongated and sharpened, this could be because of the C-H stretching off C=O and/or CH 3 of functional groups. At absorption peak cm -1 there was elongation in the peak due to the stretch in the C=O functional group of the carboxylic acids. It was noted also that the peak at cm -1 was shifted to cm -1 and the peak at cm -1 shifted to cm -1 and this was due to the stretching of 167

4 C-O of the functional groups. Peak at cm -1 also has an elongation and this might be because of the N=O bending in the functional groups. Another change was noted on the natural composition of Moringa oleifera leaves which is the existence of peaks at wave number of cm -1, cm -1, and 1032 cm -1. The repeated shift due to the C-O stretching suggests that C-O might be a functional group that Cd (II) can bind and react with it. In addition, it can be said that the shift in the absorption peaks generally observed and might indicate the existence of Cd (II) binding process on the surface of the Moringa oleifera leaves. The obtained results were in agreement with [10] results with some differences, and this might be because of different source of Moringa oleifera leaves. Fig. 3. 1D FTIR for a comparison of the transmittance of Moringa oleifera leaves before and after biosorption of Cd (II). IV. CONCLUSION This research work has focused on using Moringa oleifera leaves as a natural (without any modification or any kind of chemical treatment), environmentally friendly biosorbent for Cd (II) removal from water. Moringa oleifera leaves can be considered as an easily, locally available, low-cost adsorbent and has a considerable high biosorption capacity. It might be considered as an alternative adsorbent for Cd (II) and other heavy metals removal in water treatment. Therefore, Moringa oleifera leaves can be considered for adsorption of Cd (II) from water and further studies can be carried out to improve the performance of Moringa oleifera leaves by certain process for less dosage applications. ACKNOWLEDGMENT The authors would like to thank Research & Innovation Department/ Universiti Malaysia Pahang / Malaysia, for financial support to publish this paper under grant #: RDU REFERENCES [1] G. A. 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Awwad, "Biosorption of Cadmium (II) from Aqueous Solutions by Prunus vium Leaves," American Journal of Environmental Engineering, vol. 2, pp , [20] N. A. Eman, A. M. Suleyman, M. S. Hamzah, M. A. Zahangir, and M. S. Ramlan, "Production of natural coagulant from Moringa oleifera seed for application in treatment of low turbidity water," Journal of Water Resources and Protection, vol. 2, pp , [21] S. Kawamura, "Effectiveness of natural polyelectrolytes in water treatment," American Water Works Association, vol. 83, pp , Eman N. Ali was born in Baghdad, Iraq on 29 January, She got the bachelor degree in petroleum & mining engineering from University of Baghdad, Iraq in 1980, M.Sc. degree in chemical engineering from UKM, Malaysia in 2000, and Ph.D. degree of biotechnology engineering from IIUM, Malaysia in The major field of her study is environmental engineering (air pollution, water pollution) and Moringa oleifera 168

5 products. Sabreen Ramzi Alfarra was born in Abudhabi, UAE, on March 21, She got the B.Sc. degree in Applied Medical Science University of Sixth October, Egypt in She is an M.Sc. candidate at University Malaysia Pahang, Malaysia from September 2012 to present. Md Lutfor Rahman was born in Bangladesh. He received the B. Sc and M. Sc degree in chemistry from University of Rajshahi. Later he obtained PhD degree from UPM Malaysia. Currently Dr. Lutfor Rahman is working at UMP. Dr. Lutfor Rahman has several interests including the design and synthesis of biopolymer for heavy metal extraction from industrial waste water. Mashitah M. Yusoff got her bachelor and PhD degrees from Wichita State University (USA). She is a professor of chemistry and the deputy vice chancellor on research & innovation at Universiti Malaysia Pahang, Malaysia. 169